Lubricant compositions containing 2,4,6-tri-amino-substituted pyrimidines



United States Patent Ofiice 3,374,173 LUBRICANT COMPOSITIONS CONTAINING 2,4,6- TRI-AMINO-SUBSTITUTED PYRIMIDINES Stuart Walter Critchley, Hale Barns, and Frank Lamb, Oldham, England, assignors, by mesne assignments, to Geigy Chemical Corporation, Ardsley, N.Y., a corporation of Delaware No Drawing. Original application Nov. 9, 1964, Ser. No. 409,993, now Patent No. 3,325,496, dated June 13, 1967. Divided and this application Mar. 28, 1967, Ser. No. 626,400

Claims priority, application Great Britain, Nov. 12, 1963, 44,534/63 3 Claims. (Cl. 252-50) ABSTRACT OF THE DISCLOSURE Lubricant compositions are provided comprising as an essential lubricant ingredient 2,4,6-tri-amino-substituted pyrimidines. Such lubricant compositions are of especial value as high temperature lubricants or other functional fluids for use at high temperatures.

This application is .a division of application Serial No. 409,993 filed November 9, 1964, now Patent No. 3,325,496.

The present invention relates to lubricant compositions comprising as the essential lubricating ingredients heterocyclic organic compounds, and in particular pyrimidine derivatives, having valuable thermal stability and viscosity/ temperature properties, enabling them to be used with advantage, for example, in such lubricant compo sitions.

Accordingly, the present invention comprises compositions containing 2,4,6-tri-amino-substituted pyrimidines having the formula wherein R R and R are the same or different and each is a substituent having the formula NR R or a nitrogencontaining heterocyclic group attached at the nitrogen atom thereof to the pyrimidine ring, the groups R and R being the same or different alkyl group. More particularly R R and R represent a member from the group consisting of dialkyl amino, each alkyl of which has from 1 to 20 carbon atoms, and piperidino with the proviso that the total number of alkyl carbon atoms present is at least 16. Y

The process of producing substituted pyrimidines having the above formula, comprises reacting a 6-halo-substituted pyrimidine having the formula with the corresponding substituted amine R H, where R R and R have their previous significance and X is a halogen atom.

Preferably groups R and R are straight or branchedchain alkyl groups containing from one to twenty carbon atoms, for example, methyl, ethyl, n-propyl, n-butyl, nhexyl, n-octyl, 2-ethylhexyl, n-decyl or n-dodecyl groups; it is particularly preferred that either or both of R and R are straight-chain alkyl groups containing from one to twenty carbon atoms. If one or more of the groups R R and R is a nitrogen-containing heterocyclic groups, this may be, for example, a piperidino group. The total number of alkyl carbon atoms present is at least 16. The halogen X may be fluorine, bromine, or iodine, but is preferably chlorine.

The substituted pyrimidines may be produced by contacting the 6-halo-substituted pyrimidine with the substituted amine in the presence of a compound capable of acting as a binding agent for the hydrogen halide formed by the reaction, for example an alkali metal carbonate. The reaction is conveniently carried out at an elevated temperature, preferably at a temperature in the range from to 300 C. The reaction may be effected at substantially atmospheric pressure, but a superatmospheric pressure may in some cases be employed to advantage; for instance, if the normal boiling point of the amine is below 200 C., a sufficiently high reaction temperature may not be attainable at atmospheric pressure for completion of the reaction and it is then preferred to conduct the process at a superatmospheric pressure. For instance, if 2:4-di(di-n-butylamino)-6-chloro-pyrimidine is heated with di-n-butylamine (normal boiling point C.) or with piperidine (normal boiling point 106 C.) at atmospheric pressure, the product may be contaminated with unreacted starting material, although the corresponding reaction at atmospheric pressure with di-n-pentylamine (normal boiling point 203 C.) proceeds substantially to completion. However, by operating the process at a superatmospheric pressure, preferably at a pressure of from 1.5 to 20 atmospheres, the reaction with such lower-boiling amines can be satisfactorily effected.

The desired 2:4:6-substituted pyrimidine may be separated from the reaction product by conventional methods. For example, the reaction product may be treated by a procedure comprising filtration and fractional distillation of the filtrate, preferably under an inert atmosphere, to yield the desired compound.

The 6-halo-substitutecl pyrimidines reacted with the substituted amine may be prepared, for example, by reacting a 2 z4z6-trihalo-substituted pyrimidine having the formula:

with the same or different amines having the formula R H and R H, the groups X attached to the 2-, 4- and 6-positions in the pyrimidine ring being the same or different halogen atoms, X having its previous significance. The 2z4z6-trihalo-substituted pyrimidine may be, for example, 2:4;6-trichloro-pyrimidine, which may be prepared by reacting phosphorus oxychloride and NzN-dimethyl-phenylamine with barbituric acid.

The reaction may be carried out, for example, by con.- tacting the 2:4:6-trihalo-substituted pyrimidine with the amine (where R H and R -H represent one and the same amine) in the presence of alkali or other compound capable of binding hydrogen halide eliminated in the reaction, for instance an alkali metal hydroxide or carbonate. The reaction is conveniently effected in the presence of water, dioxane or other polar solvent, and it is desirable to employ three moles of the amine for every mole of the 2:4:6-trihalo-substituted pyrimidine. If R H and R H represent two different amines, the reaction may be carried out by contacting the trihalo-pyrimidine with an equimolar proportion of the first amine at a temperature not exceeding C., and preferably at a temperature in the range from -10 C. to +10 C., for example by cooling the reactants in an ice/ salt cooling bath. The resulting mixture may then be treated with alkali or other hydrogen halide-binding compound and allowed to react for one hour at a more elevated temperature, for example at C. The second amine is then added conveniently at 20 C. and preferably employing two moles of the second amine for every mole of the 2:4:6-trihalo-pyrimidine originally taken. The mixture may then be heated, for instance for twelve hours at 100 C., with further hydrogen halide-binding compound.

The 6-halosubstituted pyrimidine produced may be recovered, if desired, by conventional methods, for example, by solvent extraction and fractional distillation under an inert atmosphere. Instead of recovering the pure 6-halosubstituted compound, the crude reaction product containing it, if desired after partial purification, may be emloyed in subsequent reaction to produce the desired 2:4:6- tri-amino-substituted pyrimidine of the invention.

The desired 2:4:6-tri-amino-substituted pyrimidines may also be produced by reacting one molar proportion of the corresponding 2:4z6-trihalo-substituted pyrimidines directly with at least three molar proportions of the amine or amines R H, R H and R H. The reaction is preferably effected at an elevated temperature and at substantially atmospheric or at a superatmospheric pressure. A compound, such as an alkali metal carbonate, may be advantageously added to act as binding agent for hydrogen halide formed during the reaction.

The present invention comprises formulations containing the 2:4:6-tri-amino-substituted pyrimidines and in particular formulations containing the compounds for use as lubricants or other functional fluids. Pyrimidine derivatives of the type described may with advantage be blended with conventional antioxidants such as phenyl a-naphthylamine or other di-arylamines, or hindered phenols such as 2:6-di-tertiarybutyl-4-methyl-phenol, together, if desired, with metal corrosion inhibitors such as benzo-triazole. The 2:4:6-tri-amino-substituted pyrimidines have been found to have good thermal stability while at the same time possessing good viscosity/ temperature properties, and the 2:4: 6-tri-amino-substituted pyrimidines therefore have especial value as high temperature lubricants or other functional fluids for use as high temperatures.

The following examples further illustrate the present invention. Parts by weight shown therein bear the same relation to parts by volume as do kilograms to litres. Percentages are expressed by weight unless otherwise stated.

Example 1 (A) Into a vessel fitted with an efiicient stirrer, thermometer pocket, dropping funnel and reflux condenser were placed 120 parts by volume of dioxan and 200 parts by volume of water. After cooling the solution to a temperature not exceeding 10 C. using an ice/ salt cooling bath, 55 parts by weight of 2:4: 6-trichloropyrimidine were added and gradual addition of di-n-butlamine was commenced.

When 38.7 parts by weight of the di-n-butylamine had been added, 12 parts by weight of sodium hydroxide dissolved in 20 parts by volume of water were gradually added so as to keep the mixture slightly alkaline. After the addition of sodium hydroxide was complete, the cooling bath was removed and the mixture stirred for 1 hour. 77.4 parts by weight of di-n-butylamine were added in one portion, and the temperature raised to the boiling point of the mixture (about 0). During the next 12 hours, 12 parts by weight of sodium hydroxide dissolved in 20 parts by volume of water were added in portions to the mixture which was heated and stirred under reflux.

The cold reaction mixture was extracted with diethyl ether, and the ether extract was washed with water and dried with anhydrous sodium sulphate. Solvent was removed and the crude product was distilled under nitrogen.

The product obtained was 91 parts by weight of the yellow mobile liquid 2:4-bis-di-n-butylamino-6-chloropyrimidine having boiling range to 192 C. at 1.4 millimeters of mercury pressure and the following elemental analysis:

Found: C, 65.3%; H, 10.5%; N, 15.1%; Cl, 9.5%. Calculated: C, 65.2%; H, 10.1%; N, 15.2%; C1, 9.5%.

The yield was 83% theoretical.

(B) 73.7 parts by weight of this product were introduced with 73.6 parts by weight of di-n-hexylamine and 27.6 parts by weight of anhydrous potassium carbonate, into a reactor fitted with a stirrer, nitrogen inlet and refiux condenser. A nitrogen stream was maintained passing through the reactor and the temperature of the stirred contents was kept at 210 C. to 230 C. for 24 hours. After allowing to cool, the reaction mixture was diluted with benzene and filtered. Solvent was removed from the filtrate and the crude product was purified by distillation under nitrogen.

The product, after being twice distilled under nitrogen, was the red brown liquid 2:4-bis-(di-n-butylamino)-6-din-hexylamino-pyrimidine, having boiling point 217 to 221 C. at 0.3 millimeter of mercury pressure and the following elemental analysis:

Found: C, 74.1%; H, 12.1%; N, 13.6%. Calculated: C, 74.2%; H, 12.2%; N, 13.5%.

The yield was 75% theoretical, based on the product from the second distillation.

Example 2 The procedure described in Example 1B was carried out using di-n-decylamine as the amine.

The product, after being twice distilled under nitrogen, was the red brown liquid 2:4-bis-(di-n-butylamino)-6-din-decylamino-pyrimidine, having boiling point 250 to 270 C. at 0.003 tto 0.005 millimeter of mercury pressure and the following elemental analysis:

Found: C, 76.6%; H, 12.7% N, 10.6%; Calculated: C, 76.3%; H, 12.6%; N, 11.1%

The yield was 57% theoretical, based on the product from the second distillation.

Example 3 The procedure described in Example 1B was carried out using di-n-dodecylamine as the amine.

The product after being twice distilled under nitrogen, was the red brown liquid 2:4-bis-(di-n-butylamino)-6-din-dodecylamino-pyrimidine, having boiling point 252 C. to 258 C. at 0.004 to 0.005 millimeter of mercury pressure and the following elemental analysis:

Found: C, 77.1%; H, 12.8%; N, 10.0%. Calculated: C, 77.2%; H, 12.7%; N, 10.2%.

The yield was 40% theoretical, based on the product from the second distillation.

Example 4 The procedure described in Example 1A was carried out using di-n-propylamine instead of the di-n-butylamino, and using the 2:4-bis-(di-n-propylamino-6-chloro-pyrimidine as the 6-halo-pyrimidine and di-n-hexylamine as the amine in the procedure described in Example 1B.

The product, after being twice distilled under nitrogen, was the red brown liquid 2:4-bis-(di-n-propylamino)-6- di-n-hexylamino-pyrimidine, having boiling point 200 to Example 5 (A) Into a reactor fitted with a stirrer, thermometer and reflux condenser were placed 250 parts by volume of dioxan and 150 parts by volume of water. After cooling this solution to below C. with an ice/salt cooling bath, 259 parts by weight of 2:4:6-trichloro-pyrimidine were added and gradual addition of diethylamine was commenced. When 103 parts by weight of the amine had been added, an aqueous solution of 56.5 parts by weight of sodium hydroxide in 100 parts by volume of water were gradually added so as to keep the mixture just alkaline. After all the sodium hydroxide solution had been introduced, the mixture was maintained below 10 C. with stirring for 1 hour.

The cooling bath was then removed, 365 parts by weight of di-n-butylamine were added in one portion and the mixture was boiled under reflux, 56.5 parts by weight of sodium hydroxide in 100 parts by volume of water were added in portions during the next 12 hours to the stirred refluxing mixture.

After cooling, the reaction mixture was extracted with diethyl ether, and the ether extract was washed with water and dried with anhydrous sodium sulphate. Solvent Was removed and the crude product was distilled under nitrogen.

The product obtained was 370 parts by weight of the yellow mobile liquid diethylaminodi-n-buttylamino-6- chloro-pyrimidine having boiling point 142 to 152 C. at 0.4 millimeter of mercury pressure and elemental analysis:

Found: C, 61.4%; H, 9.4%; N, 18.0%; C1, 11.1%. Calculated: C, 61.5%; H, 9.3%; N, 17.9%; C1, 11.4%.

The yield was 84% theoretical. The product may be Z-dietthylamino-4-di-n-butylamino-6-chloro-pyrimidine or 2-di-n-butylamino-4-diethylamino-6-chloro-pyrimidine or a mixture of the two compounds.

(B) The procedure described in Example 1B was carried out using the product of Example 5A as the 6-halopyrimidine.

The product was the red brown liquid diethylamino-din-butylamino-6-di-n-hexylarnino-pyrimidine having boiling point 200 to 202 C. at 0.3 millimeter of mercury pressure and the elemental analysis:

Found: C, 72.9%; H, 11.6%; N, 15.1%. Calculated: C, 72.9%; H, 11.8%; N, 15.3%.

The yield was 67% theoretical. The product may be 2 diethylamino 4 di-n-butylamino-6-di-n-hexylaminopyrimidine or 2-di-n-butylamino-4-diethylamino-6di-nhexylamino-pyrimidine or a mixture of the two compounds.

Example 6 The procedure described in Example 1A was carried out, using, instead of the di-n-butylamine, an equimolar mixture of diethylamine, di-n-propylamine and di-n-butylamine.

The product was a liquid having boiling point range 156 to 166 C. at 0.4 millimeter of mercury pressure and the elemental analysis:

Found: C, 63.5%; H, 9.4%; N, 16.9%; Cl, 10.6%. Calculated: C, 61.0%; H, 9.2%; N, 17.8%; C1, 11.6%.

The yield was 65% theoretical.

(B) The procedure described in Example 1B was carried out using the product of Example 6A as the 6-halopyrimidine.

The red brown liquid product, after being twice distilled under nitrogen, was the corresponding 6-di-n-hexylamino-pyrimidine mixture having boiling range 200 to 6 216 C. at 0.5 millimeter of mercury pressure and the elemental analysis:

Found: C, 72.8%; H, 12.0%; N, 15.5%. Calculated: C, 72.9%; H, 11.8%; N, 15.3%.

The yield was 72% theoretical, based on the product from the first distillation.

Example 7 (A) The procedure described in Example 6A was carried out using instead of the amine mixture there specified, an equimolar mixture of di-n-propylamine, di-nbutylamine and di-n-pentylamine.

The product was a liquid having boiling range 178 to 195 C. at 0.6 millimeter of mercury pressure and the elemental analysis:

Found: C, 65.2%; H, 10.1%; N, 15.0%; C1, 9.5%. Calculated: C, 65.2%; H, 10.1%; N, 15.2%; C1, 9.6%.

The yield was 68% theoretical.

(B) The procedure described in Example 6B was carried out using the product of Example 7A as the 6- halo-pyrimidine.

The red brown liquid product, after being twice distilled under nitrogen, was the corresponding 6-di-n-hexylan1ino-pyrimidine mixture having boiling range 210 to 235 C. at 0.5 to 0.7 millimeter of mercury pressure and the elemental analysis:

Found: C, 73.3%; H, 11.9%; N, 14.1%. Calculated: C, 74.2%; H, 12.2%; N, 13.6%.

The yield was 65% theoretical, based on the product from the second distillation.

Example 8 parts by weight of 2:4-bis-di-n-butylamino-6-chloropyrmidine, parts by weight of di-n-butylamine and 41.4 parts by weight of anhydrous potassium carbonate were placed in a stainless steel autoclave fitted with a mechanical stirrer. The autoclave was sealed, flushed out several times with nitrogen and then pressurised with about 10 atmospheres of nitrogen. Stirring was com menced and the temperature of the mixture was raised over 5 hours to 200 to 240 C. and maintained within this temperature range for 24 hours, the pressure being about 30 atmospheres.

The reactor and contents were then allowed to cool and the reaction mixture was diluted with chloroform. The mixture was filtered and the residue washed with chloroform. After removing chloroform from the filtrate, the crude product was distilled to give 90 parts by weight of 2:4:6-tris-di-n-butylamino-pyrimidine, having boiling point to 194 C. at 0.3 millimeter of mercury pressure; the yield was 65 theoretical.

After further purification by re-distillation, the product was a red brown liquid. By dissolving in petroleum ether (boiling range 60 to 80 C.), passing through a column of alumina, and removing the solvent, 2:4:6-tris-di-nbutylamino-pyrimidine was obtained as a yellow liquid, having the elemental composition:

Found: C, 72.6%; H, 11.9%; N, 15.5%. Calculated: C, 72.9%; H, 11.8%; N, 15.3%.

Example 9 The procedure described in Example 8 was carried out using piperidine instead of the di-n-butylamine.

The product was 2:4-bis-di-n-butylamino-6-piperidinepyrimidine, a red liquid having boiling point 210 to 216 C. at 0.3 millimeter of mercury pressure and elemental analysis.

Found: C, 72.2%; H, 11.2%; N, 16.8%. Calculated: C, 72.0%; H, 11.3%; N, 16.7%.

Example 10 36.7 parts by weight of 2:4:6-trichloro-pyrimidine, 148 parts by weight of di-n-hexylamine and 82.8 parts by weight of anhydrous potassium carbonate were placed in a reactor fitted with a nitrogen inlet, stirrer and re- 7 flux condenser. A stream of nitrogen was continuously passed through the reactor during reaction; stirring was commenced and the temperature of the reactor contents was gradually raised over several hours by means of an air bath to about 250 C. and the reaction mixture was thus heated for 24 hours.

102 parts by weight of the product 2:4:6-tris-di n-hexyl amino-pyrimidine, was recovered as described in Example 1 and was a liquid having boiling range 242 to 260 C. at 0.5 millimeter of mercury pressure; the yield was 81% theoretical. On being re-distilled and treated with alumina, as described in Example 8, the compound was obtained as a yellow liquid having boiling range 260 to 270 C. at 0.5 millimeter of mercury pressure, solidifying to a waxy solid after standing for several weeks at room temperature. The elemental analysis was as follows.

Found: C, 76.2%; H, 12.5%; N, 11.3%. Calculated: C, 76.5%; H, 12.6%; N, 11.1%.

Example 11 The procedure described in Example 1A was carried out, using diethylamine instead of the di-n-butylamine there used. The product was 2:4-bis-diethylamino-6 chloropyrimidine having boiling range 123 to 127 C. at 0.5 millimeter of mercury pressure. The yield was 82% theoretical.

This intermediate product was then subjected to the procedure described in Example 1B. The product was 2:4 bis diethylamino 6 di-n-hexylaminopyrimidine, having boiling point 192 to 194 C. at 0.5 millimeter of mercury pressure and the following elemental analysis.

Found: C, 71.0%; H, 11.7%; N, 17.3%. Calculated: C, 71.1%; H, 11.7%; N, 17.3%.

The yield Was 86% theoretical.

Example 12 The procedure described in Example 1A was carried out using di-n-pentylamine instead of the di-n-butylamine there used. The product was 2:4-bis-din-pentylamino-6- chloropyrimidine having boiling range 178 to 184 C. at 0.5 millimeter of mercury pressure. The yield was 69% theoretical.

This intermediate product was then subjected to the procedure described in Example 1B, using di-iso-pentylamine instead of the di-n-hexylamine there used. The product was 2:4:6-tris-di-n-pentylaminopyrimidine having boiling point 212 to 219 C. at 0.25 millimeter of mercury pressure and the following elemental analysis.

Found: C, 74.4%; H, 12.3%; N, 12.9%. Calculated: C, 74.8%; H, 12.4%; N, 12.8%.

The yield was 83% theoretical.

Example 13 The procedure described in Example 1A was carried out using di-iso-pentylamine instead of the di-n-butylamine there used. The product was 2:4-bis-di-iso-pentylamino-6-chloropyrimidine, having boiling range 184 to 187 C. at 0.4 milimeter of mercury pressure and the following elemental analysis:

Found: 67.2%; H, 10.9%; N, 13.8%; C1, 8.3%. Calculated: C, 67.8%; H, 10.6%; N, 13.2%; Cl, 8.4%.

The yield was 85% theoretical.

This intermediate product was then subjected to the procedure described in Example 1B. The product was 2:4-bis-di-iso pentaylamino 6-di-n-hexylamino-pyrimidine having boiling point 235 to 239 C. at 0.2 millimeter of mercury pressure and the following elemental analysis:

Found: C, 75.1%; H, 12.5%; N, 12.3%. Calculated: C, 75.3%; H, 12.5%; N, 12.2%.

The yield was 92% theoretical.

The 2:4:6-tri-amino-substituted pyrimidines have been found to have good thermal stability, as measured, for

instance, by the isoteniscope method (Blake et al., Journal of Chemical and Engineering Data, 1961, volume 6, No. 1 at page 87). In this test, a small sample (2 to 4 milliliters) of the compound is maintained at a series of temperatures. The rate of increase of vapor pressure (dp/dt) is determined at each temperature, T. The values of log dp/a't are plotted graphically against the corresponding values of UT and the temperature at which the rate of of increase of vapor pressure is 0.014 millimeter of mercury per second is taken as the decomposition point. The decomposition points of some of the 2:4:6-tri-arninosubstituted pyrimidines produced in the foregoing examples are given in the following table.

Decom Viscosity in A.S.T.M. solidification Compound of position centistokes Slope, or gelation Example No. point 210 to temperature 0.) 210 F. F. 100 F. C.)

In the table, the A.S.T.M. slope referred to is the slope of the curve plotted between any two temperatures on A.S.T.M. viscosity/temperature chart D.341. The solidification or gelation' temperature referred to in the table is determined as follows:

10 to 15 milliliters of the test fluid are stored in a refrigerator for 24 hours at 0 C., then examined visually, for changes in appearance, for instance, cloudiness, crystalinity, or partial or complete solidification. This is followed by consecutive 24 hour storage periods at 10, 20, 30, -40, -54, 40, 30, 20, 10 and 0 C. with examinations after each 24 hours. By this test it is possible to evaluate the low temperature properties of lubricants, especially when materials which are subject to supercooling are to be examined.

From the data given in this table, it is clearly evident that the 2:4:6-triamino-substituted pyrimidine compounds have good viscosity/ temperature properties, while at the same time possessing high thermal stability. The compounds are, therefore, valuable lubricants or other functional fluids, alone or in admixture with other fluids, antioxidants, anticorrosion agents or other conventional additives.

As an instance of the excellent lubricant properties of the compounds, the results of lubricity tests carried out on a typical compound, namely that of Example 5, are given below. The results were obtained from the Shell 4-ball half hour wear test. The test conditions were as follows:

Duration: 30 minutes.

Ambient temperature: 21 C.

Half-inch Grade ASKF steel ball bearings used. Speed of rotation: 1420 revolutions per minute.

The results of the test were as follows:

Scar diameter (1 kilogram load): 0.151 millimeter. Scar diameter (40 kilograms load): 0.548 millimeter.

Having thus disclosed the invention, what is claimed is:

1. A lubricant fluid composition comprising as the essential lubricating ingredient a 2, 4, 6-tri-amino-substituted pyrimidine of the formula wherein each of R R and R is a member selected from the group consisting of dialkyl amino, each alkyl of which has from 1 to 20 carbon atoms, and piperidino with the proviso that the total number of alkyl carbon atoms present is at least 16 and further comprising a minor amount of a member selected from the group consisting of an antioxidant and a metal corrosion inhibitor compatible with said lubricating ingredient.

2. A lubricant fluid composition as in claim 1 wherein at least 1 alkyl group is present which is a member selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl and n-dodecyl.

References Cited UNITED STATES PATENTS Morgan 252---50 X Cyba et al. 2S2--50 X Hughes 25250 X Cupper et al. 252-50 X Critchley et al. 260-256.4

3. A lubricant fluid composition as in claim 1 wherein 10 DANIEL WYMAN Primary Examiner PATRICK =P. G ARVIN, Examiner.

at least 1 of the groups R R and R is piperidino. 

